Process for dyeing paper

ABSTRACT

The cationic or basic dyes of formulae (1) and (2) cited in claim 1 are particularly suitable for dyeing paper. 
     These dyes dye paper in a yellow, orange or brown shade having good fastness properties.

The present invention relates to a process for dyeing paper as well asto novel cationic or basic azo dyes used in said process and which arefree of sulfonic acid groups.

It is the object of this invention to provide a process for dyeingpaper, which process comprises treating the paper with a dye of formula##STR1## wherein X and Y are each independently of the other hydrogen,halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ alkylcarbonylamino,arylcarbonylamino, ureido or arylureido,

R_(l) is hydrogen, unsubstituted or substituted alkyl or aryl, or hasthe meaning of R₂,

R₂ is a cationic or protonisable radical, or wherein

R₁ and R₂, together with the linking N atom, form an unsubstituted orsubstituted 5-, 6-, or 7-membered ring which may contain further heteroatoms,

R₃ is hydrogen, halogen, C₁ -C₄ alkyl or C₁ -C₄ alkoxy,

W is a radical of formula ##STR2## wherein K is a coupling component,

Z is a linking group,

A is O, S or NH, and

R₄ and R₅ are each independently of the other hydrogen, halogen, C₁ -C₄alkyl or C₁ -C₄ -alkoxy.

Alkyl radicals in this specification will be quite generally understoodas meaning straight-chain, branched or cyclic alkyl groups. Cycloalkylpreferably contains 5 to 8 carbon atoms, and open-chain alkyl preferablycontains 1 to 8, most preferably 1 to 4, carbon atoms.

Unbranched or branched open-chain alkyl will typically be: methyl,ethyl, n- and isopropyl, n-, sec- or tert-butyl, n- and isopentyl, n-and isohexyl or 2-ethylhexyl.

These alkyl radicals may carry one or more than one substituent, e.g.,those selected from the group consisting of hydroxy, carboxy, halogen,cyano, C₁ -C₄ alkoxy, hydroxy-substituted C₁ -C₄ alkoxy, amino,alkylamino, dialkylamino, aminocarbonyl, phenyl, phenoxy andphenylaminocarbonyl, in which three last mentioned radicals the phenylgroup may in turn be substituted by C₁ -C₄ alkoxy, C₁ -C₄ alkoxy orphenoxy.

Illustrative examples of suitable radicals of this kind are:hydroxyethyl, 2-hydroxyprop-1-yl, 1-hydroxyisopropyl,2-hydroxyisopropyl, 2,3-dihydroxyprop-1-yl, methoxyethyl, ethoxymethyl,methoxycarbonyloxyethyl, chloroethyl, cyanoethyl, benzyl, 1-phenylethyl,2-phenylethyl, dimethylaminoethyl, diethylaminoethyl,hydroxyethylaminoethyl, dihydroxyethylaminoethyl, methoxycarbonylethylor aminocarbonylethyl.

Cycloalkyl is in particular cyclopentyl and cyclohexyl; and the suitablesubstituent is in particular C₁ -C₄ alkyl, especially CH₃.

Suitable alkoxy radicals are preferably those containing 1 to 4 carbonatoms, typically methoxy, ethoxy, propoxy, isopropoxy, n-butoxy,isobutoxy or tert-butoxy. These alkoxy radicals may be substituted,conveniently by the radicals cited as substituents of the alkyl groups,preferably by hydroxy or C₁ -C₄ alkoxy. Illustrative examples ofsubstituted alkoxy radicals are hydroxyethoxy, methoxyethoxy,2-hydroxypropoxy, 1,2-dihydroxyprop-3-oxy or 1,2-dimethoxyprop-3-oxy.

Halogen will typically be taken to mean fluoro, bromo, iodo or,preferably, chloro.

Aryl radicals will be understood as meaning in this specification quitegenerally aromatic or heteroaromatic radicals, but preferably naphthylor, most preferably, phenyl radicals. All these radicals may beunsubstituted or substituted. Suitable substituents are typically C₁ -C₄alkyl, C₁ -C₄ alkoxy, bromo, chloro, nitro, cyano, carboxy or C₁ -C₄alkylcarbonylamino. The particularly preferred meaning of aryl is,however, phenyl.

X in the dyes of formulae (1) and (2) is preferably hydrogen, methyl,methoxy and chloro, and Y is preferably hydrogen, methyl, methoxy,acetylamino and chloro.

Particularly suitable radicals R₁ are C₁ -C₄ alkyl radicals and C₁ -C₄alkyl radicals which are substituted by chloro, cyano, phenyl,methoxycarbonyl, methoxycarbonyloxy, mono- or di-C₁ -C₄ alkylamino, thealkyl moieties of which mono- or di-C₁ -C₄ alkylamino groups may in turnbe substituted by hydroxy, amino or mono- or di-C₁ -C₄ alkylamino.Further preferred radicals R₁ may have the meanings cited hereinafterfor R₂.

If R₁ and R₂, together with the linking N atom, form a 5-, 6- or7-membered ring, then said ring is preferably a pyrrolidine, piperidine,morpholine or piperazine ring. The piperazine radical can be substitutedat the N atom not attached to the coupling component, typically byalkyl, arylcarbonyl or arylaminocarbonyl.

The cationic or protonisable radical R₂ is typically an amine radical ora quaternised ammonium radical which is linked to the N atom through alinking group. Said radical is preferably a radical of formula ##STR3##wherein B is an unbranched or branched alkylene radical, R₆ is hydrogenor unsubstituted or substituted alkyl,

R₇ and R₈ are each independently of the other unsubstituted orsubstituted alkyl, and

Q.sup.⊕ is a cyclic cationic radical, or wherein

R₆ and R₇, together with the linking N atom, form an unsubstituted orsubstituted 5-, 6-, or 7-membered ring which may carry futher heteroatoms, or wherein R₆, R₇ and R₈, taken together, form a pyridinium ring.

If R₆ and R₇, together with the linking N atom, form a 5-, 6- or7-membered ring, then said ring is preferably a pyrrolidine, piperidine,morpholine or piperazine ring. The piperazine radical may be substitutedat the N atom not attached to B, typically by alkyl, arylcarbonyl,arylaminocarbonyl or, preferably, by an aromatic carbocyclic orheterocyclic radical.

Suitable radicals B are preferably C₂ -C₈ alkylene radicals, in whichthe alkylene chain may be straight-chain or branched or also interruptedby linking groups such as --NH--CO--, --NH--, --O--C₆ H₄ --, --O--CO--C₆H₄ --or --O--CO--, or in which the alkylene chain is linked to theradical Q.sup.⊕ through one of these linking groups.

Particularly suitable radicals B are ethylene, n-propylene, isopropyleneor n-butylene. Among these, ethylene is particularly preferred.

Unsubstituted or substituted alkyl radicals suitable for R₆, R₇ and R₈are preferably C₁ -C₄ alkyl radicals which are unsubstituted orsubstituted by hydroxy, amino, mono-C₁ -C₄ alkylamino, di-C₁ -C₄alkylamino or phenyl.

Suitable radicals Q.sup.⊕ are typically N-C₁ -C₄ alkylpipefidinium, N-C₁-C₄ alkyl-morpholinium, N-C₁ -C₄ alkylpyrrolidinium or N-C₁ -C₄alkylpiperazinium, N-C₁ -C₄ alkyl-3-pyridinium or N-C₁ -C₄alkyl-4-pyridinium.

The preferred meanings of R₃ are chloro, methyl or methoxy; but hydrogenis preferred.

If W is a radical of formula (3), then R₃ is likewise preferably chloro,methyl or methoxy; but hydrogen is preferred.

Z is a linking group, typically -NR₉ --CO--, --CO--NR₉ --NR₉ --CO--,##STR4## or --CO--NR₉ --B₁ --NR₉ --CO--, wherein R₉ is hydrogen orunsubstituted or substituted C₁ -C₄ alkyl, B₁ is a C₂ -C₁₂ alkyleneradical, in which the alkylene chain may be straight-chain or branchedand may be interrupted by one or more than one member, preferably by oneor two members, selected from --NR₉ --, --O--and --S--, and R₃ ishydrogen, halogen, C₁ -C₄ alkyl or C₁ -C₄ alkoxy.

R₉ is preferably methyl and, most preferably, hydrogen, and R₃ ispreferably hydrogen.

B₁ is preferably unsubstituted or hydroxy-substituted C₂ -C₄ alkylene,(C₂ -C₆ alkylene)-O-(C₂ -C₆ alkylene), (C₂ -C₆ alkylene)-O-(C₂ -C₆alkylene)-O-(C₂ -C₆ alkylene) or (C₂ -C₆ alkylene)-NR₉ -(C₂ -C₆alkylene).

Among the cited linking groups Z the following are particularlypreferred: --NH--CO--, --CO--NH--NH--CO--, ##STR5## and --CO--NH--(C₂-C₄ alkylene)--NH--CO--.

In formula (3) K is a coupling component, preferably a couplingcomponent known in the chemistry of azo dyes for dyeing paper.

Preferred coupling components are: ##STR6## wherein X, Y, R₁ and R₂ havethe meanings given for formulae (1) and (2), R₁₁ is C₁ -C₄ alkyl,carboxy or K₂, R₉ is hydroxy or amino, R₉ is hydrogen or unsubstitutedor substituted C₁ -C₄ alkyl, R₁₂ is C₁ -C₄ alkyl or K₂, R₁₃ is C₁ -C₄alkyl, R₁₄ is hydrogen, unsubstituted or substituted C₁ -C₄ alkyl orunsubstituted or substituted phenyl, R₁₅ is hydrogen, chloro, cyano orcarbamoyl, R₁₆ is hydrogen, unsubstituted or substituted C₁ -C₄ alkyl orK₃, n is 1 or 2, K₁ is ##STR7## and m is 1 to 4, and R₆, R₇ and R₈ havethe meanings given for formulae (6) and (7).

Among these coupling components those of formula ##STR8## areparticularly preferred.

If W is a radical of formula (4), then R₄ and R₅ are preferably eachindependently of the other hydrogen, chloro, methyl or methoxy and, moreparticularly, R₄ is hydrogen and R₅ is hydrogen, chloro, methyl ormethoxy.

It will be readily understood that those inventive dyes containingcationic groups contain equivalent mounts of anions.

The anion An.sup.⊖ is suitably an inorganic as well as an organic anion,typically including: halide, e.g. chloride, bromide or iodide, sulfate,methyl sulfate, boron tetrafluoride, aminosulfonate, perchlorate,carbonate, bicarbonate, phosphate, phosphoromolybdate,phosphorotungstate, phosphorotungstomolybdate, benzenesulfonate,naphthalenesulfonate, 4-chlorobenzenesulfonate, oxalate, maleate,acetate, propionate, lactate, succinate, chloroacetate, tartrate,methanesulfonate or benzoate ions, or a complex anion, such as the anionof zinc chloride double salts.

The anion will usually be determined by the process for the preparationof the dyes. The dyes preferably contain the anion as chloride,hydrogensulfate, sulfate, methosulfate, phosphate, formate, lactate oracetate. The anion can be exchanged in known manner for another anion.

If the dyes of this invention carry further cationic groups, then theycontain as additional anions preferably those listed above.

A particularly preferred embodiment of the process of this inventioncomprises using a dye of formula ##STR9## wherein X and Y are eachindependently of the other hydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄alkoxy, C₁ -C₄ alkylcarbonylamino, arylcarbonylamino, ureido orarylureido,

R₁ is hydrogen, unsubstituted or substituted alkyl or aryl, or has themeaning of R₂, and

R₂ is a cationic or protonisable radical.

The dyes of formulae (9) and (10) are typically obtained by diazotising4,4'-diaminobenzanilide and coupling the diazo compound so obtained witha coupling component of formula ##STR10##

The diazotisation is carried out in known manner, typically with sodiumnitrite in acid, aqueous medium, e.g. a medium containing sulfuric acid.

The coupling of the diazotised 4,4'-diaminobenzanilide to the couplingcomponent of the above formulae is likewise carried out in known manner,typically in acid, aqueous or aqueous-organic medium, preferably in thetemperature range from -10° to 40° C., most preferably in the rangebelow 10° C. The acids used are typically hydrochloric acid, aceticacid, sulfuric acid or phosphoric acid. Diazotisation and coupling canbe carried out in a one-pot process, i.e. in the same reaction medium.

The remaining dyes used according to the practice of the invention areknown or can be prepared in per se known manner. Surprisingly, thesedyes are particularly suitable for dyeing paper, and the dyeings soobtained are distinguished in particular by good fastness to light.

The dyes may be used in accordance with all customary processes forsubstantive dyes in the paper industry, in particular for beater dyeingas well as for surface dyeing of sized and unsized paper types based onbleached and unbleached cellulose of different origin, such as softwoodor hardwood sulfite and/or softwood or hardwood sulfate cellulose. Theyare also suitable for dyeing wood pulp paper.

The dyes of formulae (9)and (10) according to this invention areparticularly suitable for dyeing paper, as they have a highsubstantivity for this substrate. There are obtained dyeings in yellowto brown and, in particular, orange, shades which have good fastnessproperties. Dyes carrying cationic charges, moreover, are especiallysuitable for dyeing wood containing paper (wood pulp). The waste-water,in most cases, is completely colourless.

The dyes of formulae (1) and (2) can be formulated to solid or liquidphysical forms and used for dyeing paper.

In powder or granular form the dyes are used preferably for batchwisebeater dyeing, in which the dye is added batchwise to the pulper,hollander or mixing chest. The dyes are preferably added as formulationswhich may contain extenders, e.g. urea as solubiliser, dextrins,Glauber's salt, sodium chloride, as well as dispersants, dust inhibitorsand chelating agents such as tetrasodium pyrophosphate.

The invention accordingly also relates to solid dye formulations fordyeing paper, which formulations contain dyes of formulae (1) or (2).

In recent years the use of concentrated aqueous solutions of dyes hasgained importance on account of the advantages which such solutions haveover dyes in powder form. The use of solutions avoids the problemsassociated with dust formation, and the dyer is relieved of thetime-consuming and often difficult operation of dissolving the dyepowder in water. The use of dye solutions has, moreover, been promotedby the development of continuous processes for dyeing paper, as in suchprocesses it is expedient to add the solution direct to the hollander orat any other suitable juncture in paper manufacture.

Hence the invention further relates to concentrated aqueous solutions ofdyes of formula (1) or (2), which solutions contain no less than 5% perweight, typically 8 to 30% by weight of dye, based on the total weightof the solution.

Concentrated aqueous solutions of dyes of formula (1) or (2) can beprepared by filtering the dye suspension obtained in the synthesis ofthe dye, if appropriate effecting deionisation, conveniently by amembrane separation method, and stabilising the solution by the additionof auxiliaries such as urea, ε-caprolactam or polyethylene glycol. Itis, however, also possible to suspend the isolated dye in hydrochloricacid, to filter the dye suspension once more and to mix the filter cakewith lithium hydroxide or a suitable amine, typically an alkanolamine,and the requisite amount of water. Finally, it is also possible to carryout the coupling in the presence of lithium hydroxide, ammonia oralkanolamine, and to deionise the synthesis solution. Such dye solutionsare suitable for dyeing paper pulp in the presence of rosin and alumsize.

The dye solutions so obtained preferably contain, per 100 parts of dye,400 to 900 parts of water, 0 to 200 parts of further auxiliaries such asurea, ε-caprolactam or polyethylene glycol as well as 0 to 400 parts ofan organic carboxylic acid, e.g. formic acid, acetic acid, propionicacid or lactic acid.

The novel aqueous concentrates, which are stable at storage temperaturesof up to -5° C., are suitable for dyeing paper on which, with or withoutthe use of a size, they give attractive yellow, orange or brown shades.

The dyes of formulae (1) and (2) can also be used for dyeing textilematerials made of cellulose, e.g. cotton, as well as for dyeing leatherand glass fibres.

In the following illustrative Examples parts and percentages are byweight.

EXAMPLE 1

22.7 parts of 4,4'-diaminobenzanilide are tetrazotised in known mannerin 500 parts of water and 50 parts of 32% hydrochloric acid with sodiumnitrite in the temperature range from 0° to 5° C. Then 34.4 parts ofN-ethyl-N-(N'-dimethyl-N'-hydroxy-ethylammonium)ethyl-1,3-toluidinechloride and 5 parts of sodium acetate are added. The pH is adjusted,with vigorous stirring, to 4.0 with 2N sodium hydroxide solution.Coupling is carried out at pH 4 to 4.5 by further addition of sodiumhydroxide solution. At the same time the temperature is raised over 2hours from 0° to 5° C. to 30° C. The partially precipitated dye iscompletely precipitated by the addition of 20 parts of sodium chlorideand the precipitate is then collected by suction filtration and dried,to give 85 parts of the dye of formula ##STR11##

The dye dyes paper in a brilliant orange shade of excellent fastness towet treatments and light. The waste-waters are colourless.

EXAMPLES 2-74

The following dyes are prepared in general accordance with the proceduredescribed in Example 1. They dye paper in yellowish to reddish orange orbrown shades having good fastness properties.

    __________________________________________________________________________     ##STR12##                                                                    Examples                                                                            R.sub.1         R.sub.2                                                 __________________________________________________________________________     2    C.sub.2 H.sub.5                                                                                ##STR13##                                               3    C.sub.2 H.sub.5                                                                                ##STR14##                                               4    C.sub.2 H.sub.5                                                                                ##STR15##                                               5    C.sub.2 H.sub.5                                                                                ##STR16##                                               6    C.sub.2 H.sub.5                                                                                ##STR17##                                               7    C.sub.2 H.sub.5                                                                                ##STR18##                                               8    C.sub.2 H.sub.5                                                                                ##STR19##                                               9    C.sub.2 H.sub.5                                                                                ##STR20##                                              10    C.sub.2 H.sub.5                                                                                ##STR21##                                              11    C.sub.2 H.sub.5                                                                                ##STR22##                                              12    C.sub.2 H.sub.5                                                                                ##STR23##                                              13    C.sub.2 H.sub.5                                                                                ##STR24##                                              14    C.sub.2 H.sub.5                                                                                ##STR25##                                              15    C.sub.2 H.sub.5                                                                                ##STR26##                                              16    C.sub.2 H.sub.5                                                                                ##STR27##                                              17    C.sub.2 H.sub.5                                                                                ##STR28##                                              18    C.sub.2 H.sub.5                                                                                ##STR29##                                              19    C.sub.2 H.sub.5                                                                                ##STR30##                                              20    C.sub.2 H.sub.5                                                                                ##STR31##                                              21    C.sub.2 H.sub.5                                                                                ##STR32##                                              22    C.sub.2 H.sub.5                                                                                ##STR33##                                              23    C.sub.2 H.sub.5                                                                                ##STR34##                                              24    C.sub.2 H.sub.5                                                                                ##STR35##                                              25    C.sub.2 H.sub.5                                                                                ##STR36##                                              26    C.sub.2 H.sub.5                                                                                ##STR37##                                              27    C.sub.2 H.sub.5                                                                                ##STR38##                                              28    C.sub.2 H.sub.5                                                                                ##STR39##                                              29    C.sub.2 H.sub.5                                                                                ##STR40##                                              30    C.sub.2 H.sub.5                                                                                ##STR41##                                              31                                                                                   ##STR42##                                                              32    C.sub.2 H.sub.5                                                                                ##STR43##                                              33    C.sub.2 H.sub.5                                                                                ##STR44##                                              34    C.sub.2 H.sub.5                                                                                ##STR45##                                              35    C.sub.2 H.sub.5                                                                                ##STR46##                                              36    C.sub.2 H.sub.5                                                                                ##STR47##                                              37    C.sub.2 H.sub.5                                                                                ##STR48##                                              38    C.sub.2 H.sub.5                                                                                ##STR49##                                              39    C.sub.2 H.sub.5                                                                                ##STR50##                                              40    C.sub.2 H.sub.5                                                                                ##STR51##                                              41    C.sub.2 H.sub.5                                                                                ##STR52##                                              42    C.sub.2 H.sub.5                                                                                ##STR53##                                              43    C.sub.2 H.sub.5                                                                                ##STR54##                                              44    C.sub.2 H.sub.5                                                                                ##STR55##                                              45                                                                                   ##STR56##                                                              46                                                                                   ##STR57##                                                                                     ##STR58##                                              47                                                                                   ##STR59##                                                                                     ##STR60##                                              48                                                                                   ##STR61##                                                                                     ##STR62##                                              49                                                                                   ##STR63##                                                                                     ##STR64##                                              50                                                                                   ##STR65##                                                                                     ##STR66##                                              51                                                                                   ##STR67##                                                                                     ##STR68##                                              52    C.sub.2 H.sub.4N(CH.sub.3).sub.2                                                              C.sub.2 H.sub.4N(CH.sub.3).sub.2                        53    C.sub.2 H.sub.4N(C.sub.2 H.sub.4 OH).sub.2                                                    C.sub.2 H.sub.4N(C.sub.2 H.sub.4 OH).sub.2              54                                                                                   ##STR69##                                                                                     ##STR70##                                              55    C.sub.2 H.sub.4NHC.sub.2 H.sub.4N(C.sub.2 H.sub.5).sub.2                                      C.sub.2 H.sub.4NHC.sub.2 H.sub.4N(C.sub.2 H.sub.5).s                          ub.2                                                    56    CH.sub.3                                                                                       ##STR71##                                              57    CH.sub.3                                                                                       ##STR72##                                              58    CH.sub.3                                                                                       ##STR73##                                              59    CH.sub.3                                                                                       ##STR74##                                              60    C.sub.3 H.sub.7                                                                                ##STR75##                                              61    C.sub.3 H.sub.7                                                                                ##STR76##                                              62    C.sub.3 H.sub.7                                                                                ##STR77##                                              63    C.sub.3 H.sub.7                                                                                ##STR78##                                              64                                                                                   ##STR79##                                                                                     ##STR80##                                              65                                                                                   ##STR81##                                                                                     ##STR82##                                              66    CH.sub.2CH.sub.2CN                                                                             ##STR83##                                              67    CH.sub.2CH.sub.2CN                                                                             ##STR84##                                              68    CH.sub.2CH.sub.2Cl                                                                             ##STR85##                                              69    CH.sub.2CH.sub.2COOCH.sub.3                                                                    ##STR86##                                              70    H                                                                                              ##STR87##                                              71    H                                                                                              ##STR88##                                              72    H                                                                                              ##STR89##                                              73    H                                                                                              ##STR90##                                              74    CH.sub.2CH.sub.2OCOCH.sub.3                                                                    ##STR91##                                              __________________________________________________________________________

EXAMPLES 75-91

The following dyes are prepared in general accordance with the proceduredescribed in Example 1. They dye paper in yellowish to reddish orange orbrown shades having good fastness properties.

    __________________________________________________________________________     ##STR92##                                                                    Ex.  R.sub.1                                                                              R.sub.2        Y          X                                       __________________________________________________________________________    75   C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.4.sup.⊕N(CH.sub.3).sub.3                                                   H          H                                       76   C.sub.2 H.sub.5                                                                       ##STR93##     H          H                                       77   C.sub.2 H.sub.5                                                                       ##STR94##     H          H                                       78   C.sub.2 H.sub.5                                                                       ##STR95##     H          H                                       79   CH.sub.3                                                                              ##STR96##     H          H                                       80   C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.4N(C.sub.2 H.sub.4NH.sub.2).sub.2                                              H          H                                       81   C.sub.2 H.sub.5                                                                       ##STR97##     OCH.sub.3  H                                       82   C.sub.2 H.sub.5                                                                       ##STR98##     OCH.sub.3  H                                       83   C.sub.2 H.sub.5                                                                       ##STR99##     OCH.sub.3  H                                       84   C.sub.2 H.sub.5                                                                       ##STR100##    OCH.sub.3  OCH.sub.3                               85   C.sub.2 H.sub.5                                                                       ##STR101##    CH.sub.3   CH.sub.3                                86   C.sub.2 H.sub.5                                                                       ##STR102##    NHCOCH.sub.3                                                                             H                                       87   C.sub.2 H.sub.5                                                                       ##STR103##    NHCOCH.sub.3                                                                             H                                       88   C.sub.2 H.sub.5                                                                       ##STR104##    NHCOCH.sub.3                                                                             H                                       89   C.sub.2 H.sub.5                                                                       ##STR105##    NHCOCH.sub.3                                                                             OCH.sub.3                               90   C.sub.2 H.sub.5                                                                       ##STR106##    NHCOCH.sub.3                                                                             OCH.sub.3                               91   C.sub.2 H.sub.5                                                                       ##STR107##    Cl         H                                       __________________________________________________________________________

EXAMPLES 92 -118

The following dyes are prepared in general accordance with the proceduredescribed in Example 1. They dye paper in yellowish to reddish orangeshades of good fastness properties.

    __________________________________________________________________________     ##STR108##                                                                   Ex. R.sub.1                                                                            R.sub.2      Y      X    Q                                           __________________________________________________________________________     92 C.sub.2 H.sub.5                                                                     ##STR109##  CH.sub.3                                                                             H    NHCH.sub.2CH.sub.2NH                         93 C.sub.2 H.sub.5                                                                     ##STR110##  CH.sub.3                                                                             H    NHCH.sub.2CH.sub.2NH                         94 C.sub.2 H.sub.5                                                                     ##STR111##  CH.sub.3                                                                             H    NHCH.sub.2CH.sub.2NH                         95 C.sub.2 H.sub.5                                                                     ##STR112##  CH.sub.3                                                                             H    NH(CH.sub.2).sub.4NH                         96 C.sub.2 H.sub.5                                                                     ##STR113##  CH.sub.3                                                                             H    NH(CH.sub.2).sub.4NH                         97 C.sub.2 H.sub.5                                                                     ##STR114##  CH.sub.3                                                                             H    NH(CH.sub.2).sub.4NH                         98 C.sub.2 H.sub.5                                                                     ##STR115##  CH.sub.3                                                                             H                                                                                   ##STR116##                                  99 C.sub.2 H.sub.5                                                                     ##STR117##  CH.sub.3                                                                             H                                                                                   ##STR118##                                 100 C.sub.2 H.sub.5                                                                     ##STR119##  CH.sub.3                                                                             H                                                                                   ##STR120##                                 101 C.sub.2 H.sub.5                                                                     ##STR121##  CH.sub.3                                                                             H                                                                                   ##STR122##                                 102 C.sub.2 H.sub.5                                                                     ##STR123##  CH.sub.3                                                                             H                                                                                   ##STR124##                                 103 C.sub.2 H.sub.5                                                                     ##STR125##  CH.sub.3                                                                             H                                                                                   ##STR126##                                 104 C.sub.2 H.sub.5                                                                     ##STR127##  CH.sub.3                                                                             H                                                                                   ##STR128##                                 105 C.sub.2 H.sub.5                                                                     ##STR129##  CH.sub.3                                                                             H                                                                                   ##STR130##                                 106 C.sub.2 H.sub.5                                                                     ##STR131##  CH.sub.3                                                                             H                                                                                   ##STR132##                                 107 C.sub.2 H.sub.5                                                                     ##STR133##  CH.sub.3                                                                             H    NCH.sub.2CH.sub.2OH                         108 C.sub.2 H.sub.5                                                                     ##STR134##  CH.sub.3                                                                             H    NCH.sub.2CH.sub.2OH                         109 C.sub.2 H.sub.5                                                                     ##STR135##  CH.sub.3                                                                             H    NCH.sub.2CH.sub.2OH                         110 CH.sub.3                                                                            ##STR136##  CH.sub.3                                                                             H    NHCH.sub.2CH.sub.2NH                        111 CH.sub.3                                                                            ##STR137##  H      H    NHCH.sub.2CH.sub.2NH                        112 C.sub.2 H.sub.5                                                                     ##STR138##  OCH.sub.3                                                                            OCH.sub.3                                                                          NH(CH.sub.2).sub.4NH                        113 C.sub.2 H.sub.5                                                                     ##STR139##  CH.sub.3                                                                             CH.sub.3                                                                            ##STR140##                                 114 C.sub.2 H.sub.5                                                                     ##STR141##  OCH.sub.3                                                                            H    NHCH.sub.2CH.sub.2NH                        115 C.sub.2 H.sub.5                                                                     ##STR142##  NHCOCH.sub.3                                                                         H                                                                                   ##STR143##                                 116 C.sub.2 H.sub.5                                                                     ##STR144##  CH.sub.3                                                                             H                                                                                   ##STR145##                                 117 C.sub.2 H.sub.5                                                                     ##STR146##  Cl     Cl                                                                                  ##STR147##                                 118 C.sub.2 H.sub.5                                                                     ##STR148##  H      H                                                                                   ##STR149##                                 __________________________________________________________________________

EXAMPLE 119

22.7 parts of 4,4'-diaminobenzanilide are tetrazotised by known methodin 500 parts of water and 50 parts of 32% hydrochloric acid with sodiumnitrite in the temperature range from 0° to 5° C. Then 15.6 parts ofN-ethyl-N-(N'-dimethyl-N'-hydroxyethylammonium)ethyl-1,3-toluidinechloride and 5 parts of sodium acetate are added. Coupling is carriedout at pH 2 to 3, which is kept constant by the addition of 4N sodiumhydroxide solution, and in the temperature range from 0° to 5° C. Whenthe coupling is complete, 14 parts of3-methyl-5-pyrazolone-1-carboxamidine, dissolved in 700 parts of waterand 160 parts of acetic acid, are added to the orange suspension. The pHis adjusted to 4.0 by addition of 4N sodium hydroxide solution, thetemperature is raised to 30° C. and the coupling is completed. The pH isthen adjusted to 10, the suspension is filtered and the residue isdried, to give 81 parts of the dye of formula ##STR150##

The dye dyes paper in a reddish yellow shade of good wetfastness andlightfastness properties. The waste-waters are colourless.

EXAMPLE 120

The general procedure of Example 119 is repeated, but first adding tothe tetrazo solution 14 parts of 3-methyl-5-pyrazolone-1-carboxamidineunder analogous conditions and coupling, then adding 15.6 parts ofN-ethyl-N-(N'-dimethyl-N'-hydroxy-ethylammonium)ethyl-1,3-toluidinechloride and coupling in analogous manner, to give the dye of formula

    __________________________________________________________________________     ##STR151##                                                                   Ex.                                                                              Q             R         Y   K                                              __________________________________________________________________________    121                                                                              CONH                                                                                         ##STR152##                                                                             H                                                                                  ##STR153##                                    122                                                                              CONH(CH.sub.2).sub.2NHCO                                                                     ##STR154##                                                                             CH.sub.3                                                                           ##STR155##                                    123                                                                              CONH                                                                                         ##STR156##                                                                             H                                                                                  ##STR157##                                    124                                                                              CONH                                                                                         ##STR158##                                                                             Cl                                                                                 ##STR159##                                    125                                                                              CONH                                                                                         ##STR160##                                                                             CH.sub.3                                                                           ##STR161##                                    126                                                                              CONH                                                                                         ##STR162##                                                                             H                                                                                  ##STR163##                                    127                                                                              CONH                                                                                         ##STR164##                                                                             CH.sub.3                                                                           ##STR165##                                    128                                                                              NHCO                                                                                         ##STR166##                                                                             CH.sub.3                                                                           ##STR167##                                    129                                                                              CONH                                                                                         ##STR168##                                                                             H                                                                                  ##STR169##                                    130                                                                              NHCO                                                                                         ##STR170##                                                                             CH.sub.3                                                                           ##STR171##                                    131                                                                              CONH(CH.sub.2).sub.2NHCO                                                                     ##STR172##                                                                             CH.sub.3                                                                           ##STR173##                                    132                                                                              CONH                                                                                         ##STR174##                                                                             H                                                                                  ##STR175##                                    133                                                                              CONH                                                                                         ##STR176##                                                                             CH.sub.3                                                                           ##STR177##                                    134                                                                              CONH                                                                                         ##STR178##                                                                             H                                                                                  ##STR179##                                    135                                                                              NHCO                                                                                         ##STR180##                                                                             CH.sub.3                                                                           ##STR181##                                    136                                                                              CONH                                                                                         ##STR182##                                                                             CH.sub.3                                                                           ##STR183##                                    137                                                                              NHCO                                                                                         ##STR184##                                                                             CH.sub.3                                                                           ##STR185##                                    138                                                                               ##STR186##                                                                                  ##STR187##                                                                             CH.sub.3                                                                           ##STR188##                                    139                                                                              CONH                                                                                         ##STR189##                                                                             H                                                                                  ##STR190##                                    140                                                                              CONH                                                                                         ##STR191##                                                                             H                                                                                  ##STR192##                                    141                                                                              CONH                                                                                         ##STR193##                                                                             CH.sub.3                                                                           ##STR194##                                    142                                                                              CONH                                                                                         ##STR195##                                                                             CH.sub.3                                                                           ##STR196##                                    143                                                                              NHCO                                                                                         ##STR197##                                                                             CH.sub.3                                                                           ##STR198##                                    144                                                                              CONH                                                                                         ##STR199##                                                                             H                                                                                  ##STR200##                                    145                                                                              CONH                                                                                         ##STR201##                                                                             CH.sub.3                                                                           ##STR202##                                    __________________________________________________________________________

which dyes paper in a reddish yellow shade of good wetfastness andlightfastness properties. The waste-waters are colourless.

EXAMPLES 121 to 145

The following dyes are prepared in general accordance with the proceduredescribed in Examples 119 and 120. They dye paper in yellow to orangeshades.

    __________________________________________________________________________     ##STR203##                                                                   Ex.                                                                              Q             R         Y   K                                              __________________________________________________________________________    121                                                                              CONH                                                                                         ##STR204##                                                                             H                                                                                  ##STR205##                                    122                                                                              CONH(CH.sub.2).sub.2NHCO                                                                     ##STR206##                                                                             CH.sub.3                                                                           ##STR207##                                    123                                                                              CONH                                                                                         ##STR208##                                                                             H                                                                                  ##STR209##                                    124                                                                              CONH                                                                                         ##STR210##                                                                             Cl                                                                                 ##STR211##                                    125                                                                              CONH                                                                                         ##STR212##                                                                             CH.sub.3                                                                           ##STR213##                                    126                                                                              CONH                                                                                         ##STR214##                                                                             H                                                                                  ##STR215##                                    127                                                                              CONH                                                                                         ##STR216##                                                                             CH.sub.3                                                                           ##STR217##                                    128                                                                              NHCO                                                                                         ##STR218##                                                                             CH.sub.3                                                                           ##STR219##                                    129                                                                              CONH                                                                                         ##STR220##                                                                             H                                                                                  ##STR221##                                    130                                                                              NHCO                                                                                         ##STR222##                                                                             CH.sub.3                                                                           ##STR223##                                    131                                                                              CONH(CH.sub.2).sub.2NHCO                                                                     ##STR224##                                                                             CH.sub.3                                                                           ##STR225##                                    132                                                                              CONH                                                                                         ##STR226##                                                                             H                                                                                  ##STR227##                                    133                                                                              CONH                                                                                         ##STR228##                                                                             CH.sub.3                                                                           ##STR229##                                    134                                                                              CONH                                                                                         ##STR230##                                                                             H                                                                                  ##STR231##                                    135                                                                              NHCO                                                                                         ##STR232##                                                                             CH.sub.3                                                                           ##STR233##                                    136                                                                              CONH                                                                                         ##STR234##                                                                             CH.sub.3                                                                           ##STR235##                                    137                                                                              NHCO                                                                                         ##STR236##                                                                             CH.sub.3                                                                           ##STR237##                                    138                                                                               ##STR238##                                                                                  ##STR239##                                                                             CH.sub.3                                                                           ##STR240##                                    139                                                                              CONH                                                                                         ##STR241##                                                                             H                                                                                  ##STR242##                                    140                                                                              CONH                                                                                         ##STR243##                                                                             H                                                                                  ##STR244##                                    141                                                                              CONH                                                                                         ##STR245##                                                                             CH.sub.3                                                                           ##STR246##                                    142                                                                              CONH                                                                                         ##STR247##                                                                             CH.sub.3                                                                           ##STR248##                                    143                                                                              NHCO                                                                                         ##STR249##                                                                             CH.sub.3                                                                           ##STR250##                                    144                                                                              CONH                                                                                         ##STR251##                                                                             H                                                                                  ##STR252##                                    145                                                                              CONH                                                                                         ##STR253##                                                                             CH.sub.3                                                                           ##STR254##                                    __________________________________________________________________________

EXAMPLES 146 to 155

The following dyes are prepared in general accordance with the proceduredescribed in Examples 119 and 120. They dye paper in yellow to orangeshades.

    __________________________________________________________________________     ##STR255##                                                                   Ex.                                                                              Q    R       Y  K                                                          __________________________________________________________________________    146                                                                              CONH                                                                                ##STR256##                                                                           CH.sub.3                                                                          ##STR257##                                                147                                                                              CONH                                                                                ##STR258##                                                                           CH.sub.3                                                                          ##STR259##                                                148                                                                              NHCO                                                                                ##STR260##                                                                           CH.sub.3                                                                          ##STR261##                                                149                                                                              NHCO                                                                                ##STR262##                                                                           CH.sub.3                                                                          ##STR263##                                                150                                                                              NHCO                                                                                ##STR264##                                                                           CH.sub.3                                                                          ##STR265##                                                151                                                                              NHCO                                                                                ##STR266##                                                                           H                                                                                 ##STR267##                                                152                                                                              CONH                                                                                ##STR268##                                                                           H                                                                                 ##STR269##                                                153                                                                              CONH                                                                                ##STR270##                                                                           CH.sub.3                                                                          ##STR271##                                                154                                                                              CONH                                                                                ##STR272##                                                                           CH.sub.3                                                                          ##STR273##                                                155                                                                              CONH                                                                                ##STR274##                                                                           CH.sub.3                                                                          ##STR275##                                                __________________________________________________________________________

EXAMPLE 156

24.5 parts of dehydrothiotoluidine are suspended in 400 parts of waterand 25 parts of 32% hydrochloric acid and then diazotised by thedropwise addition of 6.9 parts of sodium nitrite at 0° to 5° C. Then30.5 parts of N-ethyl-N'-pyridiniumethyl-1,3-toluidine chloride,dissolved in 100 parts of water, are added. Coupling is effected byaddition of 30% sodium hydroxide solution at pH 2.0-2.5, whilesimultaneously raising the temperature over 2 hours from 5° C. to 30° C.during which process the dye crystallises out. The product is collectedby suction filtration and dried, to give 50 parts of the dye of formula##STR276## which dyes paper in a brilliant orange shade of excellentwetfastness and good lightfastness properties. The waste-waters arecolourless.

EXAMPLES 157 bis 170

The following dyes are prepared in general accordance with the proceduredescribed in Example 156. They dye paper in a yellowish to reddishorange shade, likewise having good fastness properties.

    __________________________________________________________________________     ##STR277##                                                                   Ex. A    Y      R.sub.1                                                                           R.sub.2    R.sub.3                                                                           R.sub.4                                    __________________________________________________________________________    157 S    CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    ##STR278##                                                                              CH.sub.3                                                                          H                                          158 S    CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    ##STR279##                                                                              CH.sub.3                                                                          H                                          159 S    H      C.sub.2 H.sub.5                                                                    ##STR280##                                                                              CH.sub.3                                                                          H                                          160 S    H      C.sub.2 H.sub.5                                                                    ##STR281##                                                                              CH.sub.3                                                                          H                                          161 S    H      C.sub.2 H.sub.5                                                                    ##STR282##                                                                              CH.sub.3                                                                          H                                          162 S    CH.sub.3                                                                             CH.sub.3                                                                           ##STR283##                                                                              CH.sub.3                                                                          H                                          163 S    OCH.sub.3                                                                            CH.sub.3                                                                           ##STR284##                                                                              CH.sub.3                                                                          H                                          164 S    NHCOCH.sub.3                                                                         CH.sub.3                                                                           ##STR285##                                                                              CH.sub.3                                                                          H                                          165 S    Cl     CH.sub.3                                                                           ##STR286##                                                                              CH.sub.3                                                                          H                                          166 O    CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    ##STR287##                                                                              H   H                                          167 O    CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    ##STR288##                                                                              H   CH.sub.3                                   168 O    CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    ##STR289##                                                                              CH.sub.3                                                                          H                                          169 NH   CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    ##STR290##                                                                              H   H                                          170 NH   CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    ##STR291##                                                                              CH.sub.3                                                                          H                                          __________________________________________________________________________

EXAMPLES 171 to 183

The following dyes are prepared in general accordance with the proceduredescribed in Example 156. They dye paper in yellowish to reddish shades,likewise having good fastness properties.

    __________________________________________________________________________     ##STR292##                                                                   Ex.                                                                              Y     R.sub.1                                                                          R.sub.2                                                                             R.sub.3                                                     __________________________________________________________________________    171                                                                              CH.sub.3                                                                            C.sub.2 H.sub.5                                                                   ##STR293##                                                                          ##STR294##                                                 172                                                                              CH.sub.3                                                                            C.sub.2 H.sub.5                                                                   ##STR295##                                                                          ##STR296##                                                 173                                                                              CH.sub.3                                                                            C.sub.2 H.sub.5                                                                   ##STR297##                                                                          ##STR298##                                                 174                                                                              OCH.sub.3                                                                           C.sub.2 H.sub.5                                                                   ##STR299##                                                                          ##STR300##                                                 175                                                                              Cl    C.sub.2 H.sub.5                                                                   ##STR301##                                                                          ##STR302##                                                 176                                                                              NHCOCH.sub.3                                                                        C.sub.2 H.sub.5                                                                   ##STR303##                                                                          ##STR304##                                                 177                                                                              CH.sub.3                                                                            C.sub.2 H.sub.5                                                                   ##STR305##                                                                          ##STR306##                                                 178                                                                              CH.sub.3                                                                            C.sub.2 H.sub.5                                                                   ##STR307##                                                                          ##STR308##                                                 179                                                                              CH.sub.3                                                                            C.sub.2 H.sub.5                                                                   ##STR309##                                                                          ##STR310##                                                 180                                                                              CH.sub.3                                                                            C.sub.2 H.sub.5                                                                   ##STR311##                                                                          ##STR312##                                                 181                                                                              CH.sub.3                                                                            C.sub.2 H.sub.5                                                                   ##STR313##                                                                          ##STR314##                                                 182                                                                              CH.sub.3                                                                            C.sub.2 H.sub.5                                                                   ##STR315##                                                                          ##STR316##                                                 183                                                                              CH.sub.3                                                                            C.sub.2 H.sub.5                                                                   ##STR317##                                                                          ##STR318##                                                 __________________________________________________________________________

EXAMPLE 184

The dye of formula ##STR319## is also prepared in general accordancewith the procedure described in Example 1. It dyes paper in an orangeshade of good fastness properties.

EXAMPLES 185 to 196

The following dyes are prepared in general accordance with the proceduredescribed in Example 1. They dye paper in yellowish to reddish orange orbrown shades having good fastness properties.

    __________________________________________________________________________     ##STR320##                                                                   Ex.    R.sub.1                                                                             R.sub.2             Y                                            __________________________________________________________________________    185    CH.sub.3                                                                             ##STR321##         CH.sub.3                                     186    C.sub.2 H.sub.5                                                                      ##STR322##         CH.sub.3                                     187    C.sub.2 H.sub.5                                                                      ##STR323##         CH.sub.3                                     188    H                                                                                    ##STR324##         CH.sub.3                                     189    H                                                                                    ##STR325##         CH.sub.3                                     190    C.sub.2 H.sub.5                                                                      ##STR326##         H                                            191    CH.sub.3                                                                             ##STR327##         H                                            192    C.sub.2 H.sub.5                                                                      ##STR328##         H                                            193    C.sub.2 H.sub.5                                                                      ##STR329##         OCH.sub.3                                    194    C.sub.2 H.sub.5                                                                      ##STR330##         OCH.sub.3                                    195    H                                                                                    ##STR331##         OCH.sub.3                                    196    C.sub.2 H.sub.5                                                                      ##STR332##         NHCOCH.sub.3                                 197    CH.sub.3                                                                             ##STR333##         NHCOCH.sub.3                                 __________________________________________________________________________

What is claimed is:
 1. A process for dying paper which comprisestreating the paper with a dye of formula ##STR334## wherein X and Y areeach independently of the other hydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄alkoxy, C₁ -C₄ alkylcarbonylamino, arylcarbonylamino, ureido orarylureido,R₁ is hydrogen, unsubstituted or substituted alkyl or aryl,or has the meaning of R₂, R₂ is a radical of formula ##STR335## whereinB is an unbranched or branched alkylene radical, R₆ is hydrogen orunsubstituted or substituted alkyl,R₇ and R₈, are each independently ofthe other unsubstituted or substituted alkyl, and Q.sup.⊕ is a cycliccationic radical, or wherein R₆ and R₇, together with the linking Natom, form an unsubstituted or substituted 5-, 6-, or 7-membered ringwhich may contain further hereto atoms, or wherein R₆, R₇ and R₈, takentogether, form a pyridinium ring R₃ is a hydrogen, halogen, C₁ -C₄ alkylor C₁ -C₄ alkoxy, W is a radical of formula ##STR336## wherein K is acoupling component,Z is a linking group of formula --NR₉ --CO--, CO--NR₉--NR₉ --CO--, ##STR337## or --CO--NR₉ --B₁ --NR₉ --CO--, wherein R₉ ishydrogen or unsubstituted or substituted C₁ -C₄ alkylene radical, inwhich the alkylene chain may be straight-chain or branched and may beinterrupted by one or more than one member, selected from --NR₉ --,--O--and --S--, and R₃ is hydrogen, halogen, C₁ -C₄ alkyl or C₁ -C₄alkoxy, with the proviso that in the dyes having W as a radical offormula (3), R₂ is of formula (8) wherein Q.sup.⊕ is N-C₁ -C₄alkylpiperidinium, N-C₁ -C₄ alkylmorpholinium, N-C₁ -C₄alkylpyrrolidinium, N-C₁ -C₄ alkylpiperazinium, N-C₁ -C₄alkyl-3-pyridinium or N-C₁ -C₄ alkyl-4-pyridinium.
 2. A processaccording to claim 1, which comprises using a dye of formula (1) or (2),wherein X is hydrogen, methyl, methoxy or chloro.
 3. A process accordingto claim 1, which comprises using a dye of formula (1), wherein Y ishydrogen, methyl, methoxy, acetylamino or chloro.
 4. A process accordingto claim 1, which comprises using a dye of formula (1) or (2), whereinR₆, R₇ and R₈ are each independently of one another a C₁ -C₄ alkylradical which is unsubstituted or substituted by hydroxy, amino, mono-C₁-C₄ alkylamino, di-C₁ -C₄ alkylamino or phenyl, or wherein R₆ and R₇,together with the linking N atom, form a pyrrolidine, piperidine,morpholine or piperazine ring.
 5. A process according to claim 1, whichcomprises using a dye of formula (1) or (2), wherein Q.sup.⊕ is N-C₁ -C₄alkylpiperidinium, N-C₁ -C₄ alkylmorpholinium, N-C₁ -C₄alkylpyrrolidinium, N-C₁ -C₄ alkylpiperazinium, N-C₁ -C₄alkyl-3-pyridinium or N-C₁ -C₄ alkyl-4-pyridinium.
 6. A processaccording to claim 1, which comprises using a dye of formula (1) or (2),wherein B is ethylene, n-propylene, isopropylene or n-butylene.
 7. Aprocess according to claim 1, which comprises using a dye of formula (1)or (2), wherein W is a radical of formula (3).
 8. A process according toclaim 1, which comprises using a dye of formula (1) or (2), wherein R₃is hydrogen, chloro, methyl or methoxy.
 9. A process according to claim1, which comprises using a dye of formula (1) or (2), wherein R₉ ismethyl or hydrogen, and R₃ is hydrogen.
 10. A process according to claim1, which comprises using a dye of formula (1) or (2), wherein B₁ isunsubstituted or hydroxy-substituted C₂ -C₄ alkylene, (C₂ -C₆alkylene)-O-(C₂ -C₆ alkylene), (C₂ -C₆ alkylene)-O-(C₂ -C₆alkylene)-O-(C₂ -C₆ alkylene) or (C₂ -C₆ alkylene)-NR₉ -(C₂ -C₆alkylene).
 11. A process according to claim 1, which comprises using adye of formula (1) or (2), wherein W is a radical of formula (3),wherein Z is a linking group of formula --NH--CO--, --CO--NH--NH--CO--,##STR338## or --CO--NH--(C₂ -C₄ alkylene)--NH--CO--.
 12. A processaccording to claim 1, which comprises using a dye of formula (1) or (2),wherein W is a radical of formula (3), wherein K is a coupling componentof formula ##STR339## wherein X, Y, R₁ and R₂ have the meanings givenfor formulae (1) and (2), R₁₀ is C₁ -C₄ alkyl, carboxy or K₂, R₁₁ ishydroxy or amino, R₉ is hydrogen or unsubstituted or substituted C₁ -C₄alkyl, R₁₂ is C₁ -C₄ alkyl or K₂, R₁₃ is C₁ -C₄ alkyl, R₁₄ is hydrogen,unsubstituted or substituted C₁ -C₄ alkyl or unsubstituted orsubstituted phenyl, R₁₅ is hydrogen, chloro, cyano or carbamoyl, R₁₆ ishydrogen, unsubstituted or substituted C₁ -C₄ alkyl or K₃, n is 1 or 2,##STR340## and m is 1 to 4, and R₆, R₇ and R₈ have the meanings givenfor formulae (6) and (7).
 13. A process according to claim 12, whichcomprises using a dye of formula (1) or (2), wherein W is a radical offormula (3), wherein K is a coupling component of formula ##STR341## 14.A process according to claim 1, which comprises using a dye of formulae##STR342## wherein X and Y are each independently of the other hydrogen,halogen, C₁ -C₄ alkoxy, C₁ -C₄ alkylcarbonylamino, arylcarbonylamino,ureido or arylureido,R₁ is hydrogen, unsubstituted or substituted alkylor aryl, or has the meaning of R₂, and R₂ is a radical of formula (8),wherein Q.sup.⊕ is N-C₁ -C₄ alkylpiperidinium, N-C₁ -C₄alkylmorpholinium, N-C₁ -C₄ alkylpyrrolidinium, N-C₁ -C₄alkylpiperazinium, N-C₁ -C₄ alkyl-3-pyridinium or N-C₁ -C₄alkylpyridinium.
 15. Paper obtained according to the process of claim 1.16. A process according to claim 1, which comprises using a dye offormula (1) or (2), wherein R₁, is a C₁ -C₄ alkyl radical or a C₁ -C₄alkyl radical which is substituted by chloro, cyano, phenyl,methoxycarbonyl, methoxycarbonyloxy, mono- or di-C₁ -C₄ alkylamino, thealkyl moieties of which mono- or di-C₁ -C₄ alkylamino groups may in turnbe substituted by hydroxy, amino or mono- or di-C₁ -C₄ alkylamino, orwherein R₁ has one of the meanings cited in claim 1 for R₂.